Cyclopentadienyl metal compounds



United States Patent C) CY CLOPENTADTENYL METAL COMPOUNDS Richard D.Gorsich, Baton Rouge, La., assignor to Ethyl Corporation, New York,N.Y., a corporation of Delaware No Drawing. Filed Oct. 7, 1958, Ser; No.765,741

'3 Claims. (Cl. 260-429) This invention relates to cyclopentadienylmetal compounds and, more particularly, to a process for the productionof cyclopentadienyl metal halide compounds of metals of group IV-B andvanadium.

It is an object of this invention to provide a novel process forproducing cyclopentadienyl metal compounds. Another object is to providea process for compounds which are highly useful as catalyst forpolymerization of olefins, particularly when used concurrently withreducing agents, such as organometallic compounds. Anotherobject is toprovide an economical process which is adapted for large scalecommercial production and which is highly selective in the formation ofthese compounds. Other objects and. advantages of this invention willbecome more apparent in the following description and appended claims.

These and other objects of the invention are accomplished by producingcyclopentadienyl dihalo metal alcoholatesof metals of group IV-B of theperiodic table and vanadium by the reaction of a cyclopentadienyl metaltrihalide with an alcohol. (The group IV-B metals are in accordance withthe table shown in the'Handbo'ok of Chemistry and Physics, 36th Edition,Chemical Rubber Publishing Company, pages 392-393.)

More specifically, the process of this invention comprises reacting analcohol, monohydric or polyhydric, with a compound having the generalformula to form a compound having the general formula C MX A wherein Cpis a cyclopentadienyl group, including substituted cyclopentadienylgroups, M is a metal as defined above, X is a halogen and A is thecorresponding alcohol residue. Thus, with polyhydric alcohols, thecompounds made by the process of this invention, can have two ormorecyclopentadienyl metal dihalogen groups bonded to the same alcoholresidue. Moreover, the alcohol residue can contain other functional.groups, .such as halogens and nitro groups and can have ether linkages,as with the polyalkylene glycols.

More particularly, the process of this invention involves the reactionof a cyclopentadienyl metal trihalide of the metals defined above withan alcohol at a temperature .of from 5(1 to 300 C., preferably from atemperature of about 0 to 200 C. The reaction can be conducted either inthe absence or presence of an inert diluent or solvent. Generally, withthe less active alcohols, the reaction is conducted in the absence of adiluent, the alcohol itself acting as a solvent for the.cyclopentadienyl metal trihalide. hols, it is sometimes desired to usean inert diluent or solventin order to reduce the concentration of thealcohol and thus avoid any tendency of the alcohol to cleavethecyclopentadienyl radical. Likewise, with the more active alcohols, it.is preferred to avoid prolonged heat- With the more active aloo ice ingof the cyclopentadienyl metal compound in the pres ence of the alcoholto avoid such cleavage reaction.

T'y'picalexamples of compounds which are made by the process of thisinvention are cyclopentadienyl methoxy titanium dichloride,cyclopentadienyl methoxy titanium dibromide, cyclopentadienyl methoxytitanium difluoride, cyclopentadienyl ethoxy titanium dichloride,cyclopenta dienyl tertiary butoXy titanium dichloride and similaralko'xy compounds having from one to about 20 carbon atoms in the alkylgroup. Typical aryloxy cyclopenta dienyl dihalo titanium compounds arecyclopentadienyl phenoXy titanium dichloride, cyclopentadienylmethylphenoxy titanium dichloride, cyclopentadienyl ethyl= phenoxytitanium dibromide, cyclopentadienyl chlorophenoxy titanium dichloride,cyclopentadienyl cyclohexyloxy titanium dichloride, cyclopentadienylnitrophenox'y titanium dichloride, the cyclopentadienyl dichlorotitanium alcoholate of ethylene glycol (GpTiCl OCH CH OCl TiCp) themethylcyclopentadienyl dibromo titanium alcoholate of propylene glycol,the indenyl dichloro titanium alcoholate of2,2-dimethyl-l,3-propanediol, the cyclopentadienyl dichloro titaniumalcoholate of 1,3,5-pentanetriol and the corresponding alcoholates of1,10-decanediol, 1,18-bctadecanediol, the resorcinals, the catechols,and the like. The cyclopentadienyl group can contain from 5 to 20 carbonatoms but the most preferred compounds for most uses contain from 5-15carbon atoms.

In addition to the above, ether alcohols can be condensed withcyclopentadienyl titanium trihalides to form the correspondingalcoholates. Thus, the compounds of this invention include thealcoholates formed from ether alcohols such asZ-ethOXyethanol,Z-benzyloxyethanol, 2- butoxyethanol and the like. Likewise thealcoholates of this invention include. those of the glycol ethers andpolyglycol ethers, such as the alcoholates formed by reaction ofcyclopentadienyl titanium trichloride with dimethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tributylene glycol, and other similar glycol ethers having theformula ride, fluorenyl propoxy vanadium dichloride, ethylcy;

clopentadienyl tetradecyloxy vanadium dichloride, and the like.Likewise, the present invention covers the cyclopentadienyl zirconium,hafnium and vanadiumv dihalo alcoholates of monohydric and polyhydricalcohols correspondingto those discussed above.

The diluents or solvents suitable for use in the process of thisinvention are hydrocarbons, preferably aromatic hydrocarbons, ethers,including polyethers, chlorinated hydrocarbons and any other inert mediawhich is non-reactive to the reactants or products. Typical examples ofsuitablesolventsarehexane, decane, octadecane, petroleum fractions,benzene, toluene, xylenes, naphthalenes, alkyl naphthaleneacyclohexane,1,1-diclil0roethane, 1,2- dichloroethane, triohloroethylene,tetrachloroethylene, carbon tetrachloride, trichlorobenzene, chlorinatedbiphenyls', dibutyl ether, dihexyl ether, the ethylene and higheralkylene glycol ethers, the diethylene glycol dialkyl ethers, such asdiethylene glycol dimethyl ether, diethylene glycol diethyl ether,diethylene glycol di-butyl ether, diethylene glycol methylethyl etherand the like.

The higher glycol alkyl ethers are also suitable such as the triethyleneglycol or tetraethylene glycol dialkyl ethers.

The cyclopentadienyl metal trihalides can be reacted with the alcoholsin from about 0.5 to 100 mole equivalents, based on the metal halide toalcohol ratio. Preferably, the alcohol is used in at leaststoichiometric quantities and usually for monoalcoholates it is employedin excess of at least 100%. The highest ratios are generally used whenthe alcohol is being employed concurrently as a solvent. With the moreactive alcohols, a solvent is usually employed and the quantities usedare closer to equivalent amounts. 7 The cyclopentadienyl metaltrihalides employed in this invention can be made by reactingdicyclopentadienyl metal dihalides with metal halides, e.g.,bis(cyclopentadienyl) titanium dichloride is reacted with titaniumtetrachloride to form cyclopentadienyl titanium trichloride. Thesecompounds can also be made by direct halogenation of thebis(cyclcpentadienyl) metal dihalides. The bis(cyclo'pentadienyl) metaldihalides can be prepared in accordance with the procedure disclosed inBritish Patent No. 797,151 or in I. Am. Chem. Soc., vol. 76, 4281(1954).

The following examples illustrate the process of this invention.

' EXAMPLE I cyclopentadienyl methoxy titanium dichloride phere. Themelting point of the product was 89-90 C.'

The cyclopentadienyl methoxy titanium dichloride prepared as above isused in equivalent quantities with triethyl aluminum as a catalyst forpolymerization of ethylene. The polymerization can be conducted at 100C., in heptane solvent using 1000 p.s.i.g. ethylene pressure to give asolid, white polymeric product. The alcoholate of this invention givesfaster, more uniform polymerization rates and has longer catalytic lifethan when employing other titanium-containing compounds. Similar resultsare obtained with other olefins, such as propylene.

EXAMPLE II cyclopentadienyl dichloro titanium alcoholate of 2,2-dimethyl1,3-pr0panedi0l A solution of 1.7 parts of cyclopentadienyl titaniumtrichloride and about 25 parts of benzene were heated to reflux.Subsequently, 0.41 part of 2,2-dimethyl 1,3-propanediol was added to thesolution and the reaction mixture was again heated to reflux. Petroleumether (30- 60 C.) was added until the solution became cloudy, whereuponthe solution was allowed to slowly cool to room temperature and theyellow crystals were filtered ed to give 1.4 parts of thecyclopentadienyl dichloro titanium alcoholate of 2,2-dimethyl1,3-propanediol, melting point 153 -l56 C.

EXAMPLE III Cyclopentadienyl tertiary butoxy titanium dichloride Twoparts of cyclopentadienyl titanium trichloride were dissolved in 20parts of hot tertiary butyl alcohol. This mixture was then refluxed.Petroleum ether (boiling point 30-60 C.) was added to the yellowsolution which was then chilled by Dry Ice. Yellow needles were filteredofl which analyzed for cyclopentadienyl tertiary butoxy titaniumdichloride.

EXAMPLE IV Methyl cyclopentadienyl hexadecyloxy zirconium dibromideCyclopentadienyl zirconium tribromide is reacted at 180 C. with a moleequivalent of hexadecyl alcohol in diethylene glycol dimethyl ethersolvent. The product is produced in good yield and is recovered bycrystallization.

EXAMPLE V Indenyl phenoxy halfnium difluoride Indenyl hafniumtrifluoride is reacted with 1.2 mole equivalents of phenol in 6 moles ofn-hexane solvent. The reaction is conducted at 0 C. The product isrecovered by chilling the reaction solution with Dry Ice and thereafterfiltering the crystalline product.

EXAMPLE VI Ethylcyclopentadienyl cyclahexyloxy vanadium dichlorideExample I is repeated except that ethylcyclopentadienyl vanadiumtrichloride is reacted with cyclohexanol. Such example of cyclohexanolis employed in excess, the excess cyclohexanol serving as a diluent forthe reaction. The temperature of the reaction is maintained at about 120C. An excellent product yield is obtained.

EXAMPLE VII Fluorenyl zirconium dichloride alcoholates of ethyleneglycol Fluorenyl zirconium trichloride is reacted with 0.5 moleequivalent of ethylene glycol at C. to form predominately thedialcoholate. The crystalline material is recovered in accordance withthe procedure of Example I in excellent yield. When the procedure isrepeated using excess quantities of ethylene glycol, i.e., 2 moleequivalents of ethylene glycol, the product is principally themonoalcoholate.

EXAMPLES VIII-XIII Example I is repeated except that difierentreactants, alcohols and solvent are employed. The details of theseexamples is given in the following table:

Example CD Acetylcyclopentadienyl titanium tribromide Vinylcyclopentadienyl vanadium trlbr e Benzyl cyclopentadienyl titaniumtribromlde Phenyl cyclopentadienyl zirconium trichlnridn rcyclopentadienyl titanium tribromide. Oyclopentadienyl titaniumtriiodide.

In the above examples, when mole equivalents of the polyhydric alcoholsare employed the products are primarily the polyalcoholates and whenexcess quantities of the alcohol are employed, the product isprincipally the monoalcoholate.

The above examples illustrate the process of this invention conductedwith a variety of monohydric and polyhydric alcohols. When the aboveexamples are repeated using n-hexane, decanol, eicosanol, cresol,naphthol, t-butyl alcohol, benzyl alcohol, alkyl and dialkyl phenolssuch as dimethyl phenol, butylene glycol, glycerol and the like,comparable results are obtained. In general, each of the alcohols,straight chain, branched, cyclic or aromatic, containing 1-20 carbonatoms, preferably 1-10, and 1-3 hydroxyl groups can be reacted with anyone or a mixture of the cyclopentadienyl metal tnhalides used in theabove examples or those mentioned elsewhere above. Moreover, in somecases two or more alcohols can be reacted with any of the abovecyclopentadienyl metal halides above disclosed. The preferred alcoholsare hydrocarbons, i.e. contain only carbon atoms and hydrogen atoms, inaddition to the hydroxyl group or groups. However, the alcohols can besubstituted with substituents such as halogens which are inert in thereaction. The cyclopentadienyl groups used in this invention arelikewise preferably hydrocarbons but these groups can also contain othergroups which are inert in the reaction. Best results are obtained withcyclopentadienyl groups containing from 5 to about 17 carbon atoms.

I claim:

1. A process for the production of cyclopent-adienyl dihalo metalalcoholates comprising reacting at a temperature between about C. and300 C., a cyclopentadienyl hydrocarbon metal trihalide in which thecyclopentadienyl hydrocarbon group contains from 5 to about 20 carbonatoms with a hydrocarbon alcohol having from 1 to 20 carbon atoms and 1to 3 hydroxyl groups, said metal being selected from the groupconsisting of metals of group IV-B and vanadium, the cyclopentadienylhydrocarbon metal tn'halide to alcohol mole equivalent ratio being fromabout 0.5 to about 100.

2. The process of claim 1 wherein the reaction is conducted at atemperature of O to 200 C. and the quantity of alcohol is at leaststoichiometric relative to the quantity of the cyclopentadienylhydrocarbon trihalide.

3. The process of claim 1 wherein the reaction is carried out in thepresence of a solvent.

References Cited in the file of this patent FOREIGN PATENTS 793,354Great Britain Apr. 16, 1958

1. A PROCESS FOR THE PRODUCTION OF CYCLOPENTADIENYL DIHALO METALALCOHOLATES COMPRISING REACTING AT A TEMPERTAURE BETWEEN ABOUT -50* C.AND 300* C., A CYCLOPENTADIENYL HYDROCARBON METAL TRIHALIDE IN WHICH THECYCLOPENTADIENYL HYDROCARBON GROUP CONTAINS FROM 5 TO ABOUT 20 CARBONATOMS WITH A HYDROCARBON ALCOHOL HAVING FROM 1 TO 20 CARBON ATOMS AND 1TO 3 HYDROXYL GROUPS, SAID METAL BEING SELECTED FROM THE GROUPCONSISTING OF METALS OF GROUP IV-B AND VANADIUM, THE CYCLOPENTADIENYLHYDROCARBON METAL TRIHALIDE TO ALCOHOL MOLE EQUIVALENT RATIO BEING FROMABOUT 0.5 TO ABOUT 100.